CN103865058B - A kind of polyamide and preparation method thereof and Amilan polyamide resin composition - Google Patents
A kind of polyamide and preparation method thereof and Amilan polyamide resin composition Download PDFInfo
- Publication number
- CN103865058B CN103865058B CN201310525548.3A CN201310525548A CN103865058B CN 103865058 B CN103865058 B CN 103865058B CN 201310525548 A CN201310525548 A CN 201310525548A CN 103865058 B CN103865058 B CN 103865058B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- chloride
- bromide
- iodide
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polyamides (AREA)
Abstract
The present invention provides a kind of polyamide containing diamine unit and two acid units and preparation method thereof, and the fusing point of the polyamide is more than 280 DEG C;50~100 moles of % of two acid unit therein are oxalic acid units；Containing one or more in transition metal halide, alkali halide or alkaline-earth halide；Relative to the weight of polyamide, the content of metal is 100~4000ppm.It with low water absorption, high-melting-point and is detained the characteristics such as stability with good melting, and can be shaped to can be used for the synthetic resins such as automobile component, mechanical part, fiber or film etc. by the arbitrary forming method such as injection moulding.
Description
Technical field
The present invention relates to a kind of polyamide, with being related to a kind of low water absorption, high-melting-point and with good molten
Melt highly viscous polyamide for being detained stability and preparation method thereof.
Background technology
Crystallinity polyamide with nylon 6, nylon66 fiber etc. for representative, it is easy due to its excellent characteristic and melt-shaping
Property, it is widely used as dress material use, industry goods, materials and equipments fiber or general engineering plastics, still, on the other hand, also indicates that
Physical property changes caused by water suction, the problems such as deterioration in acid, the alcohol of high temperature, hot water, to seeking dimensional stability, resistance to
The requirement of medicine and the more excellent polyamide of heat resistance improves.In electrical and electronic parts field, with surface mount skill
Art（SMT）Development, high heat resistance is needed for the polyamide in the technical field, including reflow soldering heat resistance.
In this case, it is still necessary to which exploitation not only has good heat resistance, and has good dimensional stability, good mechanical properties
With the high quality polyamide of good chemical resistance.
On the other hand, it is known to use oxalic acid unit is referred to as polyoxamide as the polyamide of dicarboxylic acid units, with
Other polyamides of identical amide groups concentration compared to water absorption rate it is low, expect caused by water suction physical property change turn into
Problem, and applied flexibly at present in the unworkable field of polyamide.
Such as in bibliography S.W.Shalaby., J.Polym.Sci., 11,1 (1973), 1,6- hexamethylene diamine is as two
The polyoxamide of amine component, its fusing point（About 320 DEG C）Obvious decomposition occurs during higher, melt-processed.Disclosed for space portion
Polyoxamide（WO2008/072754）The resin of PA92/2- methyl -82, there is low water absorbable, solvent resistance and good processing
Type, but its fusing point, at 240 DEG C or so, for requiring dystectic purposes, its heat resistance is bad.For gathering grass disclosed in space portion
Acid amides（WO2011/136263）PA62/2-M52 resins, wherein the polyoxamide resin with 280 DEG C of melt point above is relatively viscous
Degree is not all improved（Relative viscosity is less than 2.05）, and during melt-processed the viscosity of polymer occur it is obvious under
Drop.For polyoxamide disclosed in space portion（JP2011236387）PA52 resins, although viscosity is improved, its is poor
Melting be detained stability the viscosity of polyoxamide resin during melt-processed will be caused to occur declining by a relatively large margin.
The content of the invention
In order to solve the melting of hard fat polyamide, to be detained stability poor and be not easy the problem of high viscosity,
The invention provides a kind of high-viscosity polyamide resin with high-melting-point, good melting anelasticity and excellent machining property.
The present invention provides a kind of polyamide containing diamine unit and two acid units, its fusing point more than 280 DEG C, its
In 50~100 moles of % of two acid units be oxalic acid unit；Contain transition metal halide, alkali halide or alkaline-earth metal
It is one or more in halide；Relative to the weight of polyamide, the content of metal is 100~4000ppm.
Above-mentioned diamine unit is preferably 1,3- propane diamine unit, Putriscine unit, 1,5- pentanediamines unit, 1,6-
Hexamethylene diamine unit, 1,7- heptamethylene diamines unit, 1,8- octamethylenediamines unit, 1,9- nonamethylene diamines unit, 1,10- decamethylene diamines, 1,11- 11
Alkane diamine unit, 1,12- dodecamethylene diamines unit, 1,13- tridecane diamines unit, 1,14- tetradecanes diamine unit, 1,15-
Pentadecane diamine unit, 1,16- hexadecanes diamine unit, 1,17- heptadecanes diamine unit, 1,18- octadecamethylene diamines unit, 2-
Methyl isophthalic acid, 5- pentanediamines unit, 2- methyl isophthalic acids, one in 8- octamethylenediamines unit, cyclohexane diamine unit or benzene dimethylamine unit
Kind is several.When the carbon number of diamine unit is less than 3, it is possible to which the viscosity for polyamide occur is difficult to improve and gather
The too high unmanageable tendency of fusing point of amide resin；When the carbon number of diamine unit is higher than 10, it is possible to polyamides occur
The relatively low tendency for causing heat resistance to reduce of the fusing point of polyimide resin.From the aspect of the crystallinity of polyamide, preferred straight chain
Diamine unit.In addition, from polyamide it is dystectic from the aspect of, the further preferred Putriscine list of diamine unit
One or more in member, 1,5- pentanediamines unit or 1,6- hexamethylene diamine unit, its content is preferably relative to diamine unit total amount
10~100 moles of %, more preferably 50~100 moles of %, it is still more preferably 80~100 moles of %, it is more further excellent
Elect 90~100 moles of % as.Diamine unit is most preferably 1,5- pentanediamine units.
The possibility of heat resistance and melt-processed in view of polyamide, the amide groups of polyamide of the invention
Content（Relative to amide groups molal quantity in 1g polyamide）Preferably 9.5mmol/g~14.5mmol/g, more preferably
10.5mmol/g~14.0mmol/g, it is still more preferably 11.0~13.0mmol/g.If amide groups content is less than
9.5mmol/g, the fusing point of polyamide is too low to cause heat resistance to decline, if amide groups content is higher than 14.5mmol/g, gather
The fusing point of acid amides is too high may to be led to not carry out melt-processed.
Two above-mentioned acid units contain oxalic acid unit, and the content of its mesoxalic acid unit is relative to the total amount of two acid units
50%~100 mole of %.Oxalic acid unit content in two acid units increases, and can reduce the water absorption rate of polyamide, and energy
Enough improve the dimensional stability of its product.Then the content of oxalic acid unit is preferably 80~100 to rub relative to two acid unit total amounts
You are %, most preferably more preferably 90~100 moles of %, 100 moles of %.Starting monomer as oxalic acid unit is not special
Limit, the one or more that can be enumerated as in oxalate diester, oxalic acid, oxalic acid acyl chlorides or oxalic acid acyl chlorides ester etc..Preferably oxalic acid
Diester.The present invention is not particularly limited for oxalate diester.The oxalate diester that can be enumerated further preferably in dimethyl oxalate,
Diethy-aceto oxalate, DPO, oxalic acid diisopropyl ester, dibutyl oxalate, di-isobutyl oxalate or oxalic acid di tert butyl carbonate
In one or more.
Two acid units beyond oxalic acid unit in two above-mentioned acid units are not particularly limited.The oxalic acid list that can be enumerated
The starting monomer of two acid units beyond member is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, nonyl
Diacid, decanedioic acid, 1,11- undecyls diacid, 1,12- dodecyls diacid, 1,13- tridecyls diacid, 1, the 14- tetradecanes
Base diacid, 1,15- pentadecyls diacid, 1,16- cetyls diacid, 1,18- octadecyls diacid or 1,19- nonadecyl
The ring-type diacid such as the aliphatic diacids such as diacid and its corresponding various ester type compounds or Isosorbide-5-Nitrae -/1,3- cyclohexane diacid and
Aromatic diacids such as its corresponding various ester type compounds or terephthalic acid (TPA) or M-phthalic acid and it is corresponding various
One or more in ester type compound.
Above-mentioned transition metal halide is not particularly limited, and can be enumerated as copper halide, manganous halide or zinc halogenation
One or more in thing etc..It is specific enumerate as：Cupric iodide, cuprous iodide, copper bromide, cuprous bromide, copper chloride, protochloride
One or more in copper, manganous chloride, manganese dibromide, manganous diiodide, zinc iodide, zinc bromide and zinc chloride.Wherein, it is preferably
One or more in cuprous iodide, cuprous bromide, stannous chloride, copper chloride, manganous diiodide or zinc iodide.Further preferably
For the one or more in cuprous iodide, manganous diiodide or zinc iodide.
Above-mentioned alkali halide is not particularly limited, and can be enumerated as：Lithium halide, sodium halide or potassium halide
One or more in.Specifically it is enumerated as：KI, KBr, potassium chloride, sodium iodide, sodium chloride, sodium bromide, lithium chloride
One or more in lithium iodide or lithium bromide.Wherein, more preferably KI, sodium iodide, KBr, sodium bromide chlorination
One or more in lithium or lithium iodide.Still more preferably be KI, sodium iodide, KBr or sodium bromide in one kind or
It is a variety of.
Above-mentioned alkaline-earth halide is not particularly limited, and can be enumerated as：Calcium halide, magnesium halide or barium halogenation
One or more in thing etc..Specifically it is enumerated as calcium iodide, calcium bromide, calcium chloride, barium iodide, barium bromide, barium chloride, iodate
One or more in magnesium, magnesium bromide or magnesium chloride.Wherein, more preferably calcium iodide, barium iodide, magnesium chloride or magnesium iodide
In one or more.Still more preferably it is the one or more in calcium iodide, barium iodide or magnesium iodide.
It is contained in transition metal halide, alkali halide or alkaline-earth halide in above-mentioned polyamide
The content of transition metal, alkali metal and/or alkaline-earth metal is 100~4000ppm, preferably 100 relative to polyamide weight
~3000ppm, more preferably 100~2500ppm.The content of transition metal, alkali metal and/or alkaline-earth metal is within the above range
When, it can further improve melting and be detained stability and the precipitation of metal or the corrosion of polymerization unit can be suppressed.Polyamide
Thermal oxidative degradation can all occur in high temperature working processes or in hot environment use for resin, and its reason is such as《polymer
degradation and stability》(vol.49,1995) described in page 127~133：It is adjacent with the nitrogen in amide groups
Methylene easily occurs electron detachment and forms free radical, because this free radical can be with the lone pair electrons on imido grpup and carbonyl
Pi bond forms stable resonant structure.Contain oxalyl amine unit, oxalyl amine unit in the Component units of the polyamide of the present invention
On adjacent two pairs of amide groups more stable resonant structure can be formed than general single amide groups, so the polyamides of the present invention
Polyimide resin is more prone to occur the adjacent methylene of nitrogen in amide groups relative to the common polyamide such as polyamide 66
Electron detachment, produce thermal oxidative degradation.So hot oxygen of the polyamide containing oxalic acid unit of more than 280 DEG C of fusing point of the present invention
Changing degraded can be effectively suppressed, it is necessary to add above-mentioned metal halide.
The molecular weight of the polyamide obtained by the present invention is not particularly limited, dense using 96% concentrated sulfuric acid solution as solvent
The polyamide sulfuric acid solution for 0.01g/ml is spent, scopes of the relative viscosity η r determined at 25 DEG C 2.05~5.00
It is interior.More preferably 2.10~4.50.Still more preferably it is 2.40~4.00.When η r are less than 2.05, molding may become
Crisp, physical property reduces.On the other hand, when η r are higher than 5.00, melt viscosity may uprise, and shaping processability is deteriorated.
The thermal characteristics of the polyamide obtained by the present invention is to use Differential Scanning Calorimeter under inert gas atmosphere, with 20
DEG C/min cooling rate drop to 30 DEG C from molten condition, then with the temperature-rise period of 20 DEG C/min of determination of heating rate
The endotherm peak temperature of appearance（Tm：Fusing point）Preferably more than 280 DEG C.Endotherm peak temperature Tm is more preferably 280 DEG C to 320
DEG C, more preferably 280 DEG C to 310 DEG C.When the temperature Tm of endothermic peak is less than 280 DEG C, the heat resistance of polymer may reduce, can not
Practical application is obtained in applied at elevated temperature environment.
The melting enthalpy change of the polyamide of gained of the invention is preferably 65~150J/g.More preferably 70~
130J/g, more preferably 80~120J/g.If its melting enthalpy, which becomes, is less than 65J/g, it would be possible to the shaping of polyamide occurs
The tendency that processing characteristics reduces.If its melting enthalpy, which becomes, is higher than 150J/g, it would be possible to occurs that polyamide crystallinity is too high to be led
The tendency for causing its impact property to decline.
The melting of the polyamide obtained by the present invention is detained stability and is characterized in：At a temperature of than fusing point high 20 DEG C
Sulfuric acid solution relative viscosity when being detained 60 minutes is stood in nitrogen atmosphere and is set to Y, the sulfuric acid solution relative viscosity before delay is set
For X when, Y/X is preferably 0.85~1.40.Further preferred 0.87~1.30, still more preferably 0.89~1.20.If Y/X
Less than 0.85, the resin during melt-processed may have obvious decomposition, have a strong impact on its mechanical performance.If Y/X is high
In 1.40, the resin during melt-processed may have obvious viscosity increase, it will increase machine-shaping difficulty.
The hygroscopicity of the polyamide obtained by the present invention is that this PA membrane that thickness is 0.1~0.5mm soaks completely
Enter in deionized water, the saturation hydroscopicity tested at 23 DEG C is preferably shorter than 4.5wt%.
The preparation method of polyamide of the present invention, it includes：
Diamine source and dicarboxylic acids source are carried out step (a) into solution or melt polymerization obtains low molecular weight prepolymer, its
50~100 moles of % of middle dicarboxylic acids unit are oxalic acid units；
Step (b) carries out melt polymerization to prepolymer or solid phase obtains polyamide；
Wherein：Transition metal halide, alkali halide, one or more are in step in alkaline-earth halide
（a）Or in step（b）Incipient stage be added in preparation process.
It is identical with the content of above diamine unit for the content in diamine source in the preparation method of the present invention.
Lower noodle producing method can be enumerated in the range of the preparation method of above-mentioned polyamide：
It is prepared by the prepolymer of preparation method 1：
The raw material monomer of polyamide is above-mentioned diamine component and dicarboxylic acid component（Dicarboxylic acid component include 50%~
100% oxalic acid composition forms）.First typically with condenser pipe reactor in add organic solvent, then add diamines into
Point, and enter line replacement with nitrogen, dicarboxylic acid component is then added again to be blended.Then start agitating and heating and be warming up to solvent time
The temperature of stream carries out reaction 3~5 hours, then filtered and with methanol or ethanol carry out 3~5 times clean, what is obtained is pre-
Polymers is dried.As organic solvent, it is not particularly limited, toluene, dimethylbenzene, trichloro-benzenes, phenol or trifluoro can be used
Ethanol etc., can be preferably toluene.
The melt polymerization of the prepolymer of preparation method 2
Prepolymer and above-mentioned metal salt component prepared by preparation method 1（The metallic atom addition weight ratio of metal salt
It is 100~4000ppm relative to polyamide weight）It is sufficiently mixed by required proportioning, is then added in reactor, is used in combination
Nitrogen enters line replacement.This reactor is placed into heater, is then begun to warm up the fusing point temperatures above for being warming up to prepolymer, is entered
Row decompression polymerase 10 .5~5 hour, final pressure is 5000~20Pa, or polymerization under atmospheric pressure is carried out under inert gas flow
0.5~5 hour.
The solid phase of the prepolymer of preparation method 3
Prepolymer and above-mentioned metal salt component prepared by preparation method 1（The metallic atom addition weight ratio of metal salt
It is 100~4000ppm relative to polyamide weight）It is sufficiently mixed by required proportioning, is then added in reactor, is used in combination
Nitrogen enters line replacement.Then carried out below its fusing point 0.5~30 hour depressurized solid phase polymerization, final pressure be 300~
20Pa, or carry out under inert gas flow the normal pressure solid phase of 0.5~30 hour.
In the heating polycondensation of above-mentioned polyamide, due to carrying out polymerisation at high temperature, thus short carbon chain is based on
Straight-chain aliphatic diamines volatilized out of polymerization system or lower boiling product the reason such as is volatilized by deamination reaction, with
The progress of polymerization, total amido amount may be reduced relative to dicarboxyl acidic group and dicarboxylic acids ester group content in polymerization system, therefore,
The stage of raw material is being added, the straight-chain aliphatic diamines for excessively adding the short carbon chain of specified quantitative in advance is controlled in polymerization system
Amido amount, for synthesize HMW polyamide for be preferable.When the short carbon chain that will be used as raw material is straight
The molal quantity of chain fatty race diamines is set to a, when the molal quantity of total dicarboxylic acid component's raw material is set into b, preferably forms raw material
It is more preferably 1.008~1.08 than being adjusted to a/b as 1.003~1.10, a/b, is still more preferably 1.01~1.05.
If a/b, less than 1.003, the total amido amount and dicarboxyl acidic group and dicarboxylic acids ester group content in polymeric system are relative few,
It is difficult to the polymer for obtaining HMW.If a/b is more than 1.10, total amido amount and dicarboxyl acidic group and dicarboxyl in polymerization system
Perester radical content is relatively excessive, it is difficult to obtains the polymer of HMW.
In the preparation method of the present invention, the transition metal halide, alkali halide or alkaline-earth halide choosing
From the one or more in the chloride, bromide or iodide of transition metal, alkali metal or alkaline-earth metal.Particular content with it is upper
The description of literary transition metal halide, alkali halide or alkaline-earth halide is identical.
Various packing materials can also be added as needed in the polyamide of the present invention, specific packing material is as follows.
Inorganic filling material is such as：Graphite, barium sulfate, calcium carbonate, antimony oxide, titanium oxide, aluminum oxide, nickel, aluminium, iron, steel, cunning
Stone, bentonite, montmorillonite, mica titanium dioxide, silica or silicate etc..For some phyllosilicates, can use
Organic ammonium salt carries out interlayer ion the silicate that organises after cation exchange.It is excellent for the appearance of polyamide
Different, the average grain diameter of inorganic filler is preferably 0.001~10 μm.If average grain diameter is less than 0.001 μm, gained polyamide
The melt processable of resin combination can significantly reduce, if in addition, particle diameter is more than 10 μm, surface of the molded article outward appearance has variation
Tendency.Its addition is preferably 0.1~200 weight portion relative to the weight portion of polyamide 100.
The fibrous filler material of organic system and the fibrous filler material of inorganic system.Fiber as organic system fills material
Material can enumerate the fully aromatic polyamide fibers such as aromatic polyamide fibers, cellulose fibre etc..Threadiness as inorganic system is filled out
Glass fibre, carbon fiber or boron fibre etc. can be included by filling material.In addition, also metallic fiber, aluminium borate, gypsum, carbonic acid
It is one or more in the inorganic compound such as calcium, sepiolite, eakleite or wollastonite whisker or acicular crystal etc..Furthermore, it is possible to
, can also be preferably relative using the chopped fiber that length is 0.05~5mm, its addition using 5~50mm of length long fibre
In 0.1~200 parts by weight of the parts by weight of polyamide 100.
The polyamide of the present invention can also be added as needed on various additives, such as weather resisting agent, the demoulding in preparing
One or more in agent or lubricant, pigment, dyestuff, plasticizer, antistatic additive, fire retardant or other polymers.Specifically,
Weather resisting agent is resorcinol system, salicylate system, enumerate BTA system, benzophenone series or amine system of being obstructed etc.；Releasing agent or lubrication
Agent is aliphatic alcohol, aliphatic amide, aliphatic bisamide, allophanamide or Tissuemat E etc.；Pigment is cadmium sulfide, phthalocyanine or carbon black
Deng；Dyestuff is nigrosine or nigrosine etc.；Plasticizer is P-hydroxybenzoic acid monooctyl ester or N-butylbenzenesulfonamide etc.；It is anti-quiet
Electric agent is alkyl sulphate type anion system antistatic additive, quaternary ammonium salt cationic system antistatic additive, polyoxyethylene sorbitan
Nonionic system antistatic additive as sugar alcohol monostearate or glycine betaine system both sexes antistatic additive etc.；Fire retardant is melamine
The hydroxide such as amine, magnesium hydroxide or aluminium hydroxide, ammonium polyphosphate, bromo polyethylene, bromo polyphenylene sulfide, the poly- carbonic acid of bromo
Ester, brominated epoxy resin or composition of bromo-derivative fire retardant and antimony oxide etc.；Other polymers are polyamide, poly- second
Alkene, polypropylene, polyester, makrolon, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, ABS resin, SAN resins or polystyrene
Deng.
In addition, in order to improve the impact property of polyamide, resistance to punching can also be added in polyamide of the invention
The packing material of hitting property, such as：By one or more in alkenes compounds and conjugated diolefin Lai equal (common) polymers.
Above-mentioned equal (common) polymers can be enumerated as ethene copolymer, conjugated diolefin homopolymer and conjugated diene
The copolymer of hydrocarbon/aromatic ethylene compound.Ethene copolymer is two membered copolymers or polynary of ethene and other cell cubes
Copolymerization.Other cell cubes can be enumerated as the alpha-olefin of carbon more than 3, non-conjugated diene hydrocarbon, vinyl acetate, vinyl alcohol, α,
Beta-unsaturated carboxylic acid and its inductor.Its addition is preferably 5~200 weight portions relative to the weight portion of polyamide 100.
If addition is more than more than 5 parts by weight, the impact of polyamide is improved significantly；If addition is less than 100
Kind amount part, be advantageous to the forming of polyamide.
The polyamide of the present invention can be spun by injection moulding, extrusion molding, blow molding, vacuum forming, melting
The arbitrary forming method such as silk or film shaping is shaped to required shape, can be used for the resins such as automobile component, mechanical part
Products formed, fiber or film etc..Specific purposes：The top of automobile engine cooling water based part, particularly radiator tank and
Pump parts such as the radiator water box part such as bottom, coolant reserve tank, water pipe, water pump shell, water pump vane, valve etc., and vapour
The part contacted in car engine with cooling water.Electrical and electronic parts be small-sized switch, switch shell, lamp socket, connector,
Housing, connector shell, IC sockets class, bobbin, bobbin cover, relay, electrical relaybox, capacitor protector, the motor of connector
Internal part, small size motor shell, gear cam, the equilibrium theory, pad, insulator, fastener, buckle, wire clamp, Caster, peace
Full cap, electronic table starter insulating element, fuse box, the shell of terminal, wheel cover, suction tracheae, bearing retainer, electric wire optical cable
Clad or fibre optics cable oversheath etc. are the electrical and electronic parts, automobile associated components, computer dependent part of representative
Part, mechanical associated components or other various uses.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not by any restriction of these embodiments.Implement
Various characteristics in example and comparative example, are determined by the following procedure.
(1) relative sulfuric acid viscosity：
Using 96% sulfuric acid as solvent, compound concentration is 0.01g/ml polyamide sulfuric acid solution, and phase is determined at 25 DEG C
To viscosity.
(2) thermal property：
Using TA DSC-Q100 analytical instrument, about 5mg samples are accurately weighed, test condition is as follows：In a nitrogen atmosphere,
The temperature (T0) that gained polyamide is warming up to the endothermic peak than occurring with 20 DEG C/min of programming rates is higher by 30 DEG C
Temperature, kept for 2 minutes at this temperature, then drop to 30 DEG C with 20 DEG C/min of cooling rate, kept for 2 minutes at 30 DEG C.
Next, the temperature Tm of the endothermic peak observed when being warming up to 20 DEG C/min of programming rate and be higher by 30 DEG C than T0 and melting
Enthalpy change（ΔHm）.（3）Stability is detained in melting
In a nitrogen atmosphere, it is heated to more than fusing point stand the sample after being kept for 60 minutes at a temperature of 20 DEG C with 0.01g/
Ml concentration, which is dissolved in 96% sulfuric acid, tests its relative viscosity（Y）, the relative sulfuric acid viscosity before delay is set to（X）, obtain sulphur
The conservation rate of sour relative viscosity（Y/X）.
(4) 23 DEG C of saturated water absorptions：
By polymer at a temperature of than fusing point high 20 DEG C hot pressing film forming, and promptly cooled down in frozen water, thickness of sample
For 0.1~0.5mm (50mm*50mm).Its weight (W1) is weighed after sample is immersed in 23 DEG C of water to constant weight, then will examination
100 DEG C of sample weighs its weight (W2) after being dried in vacuo to constant weight.Calculate water absorption rate (%)=100* (W1-W2)/W2.Referred to as explanation：
Putriscine:Purity is 98%, purchased from Sigma-Aldrich companies.
1,5- pentanediamine：Purity is 98%, purchased from TCI companies.
1,6- hexamethylene diamine：Purity is 98%, purchased from TCI companies.
Dibutyl oxalate：Analyze it is pure, purchased from Aladdin company.
1,6- adipic acid:Analyze it is pure, purchased from Aladdin company.
1,9- nonamethylene diamine:Purity is 99%, purchased from Sigma-Aldrich companies.
1,10- decamethylene diamine:Purity is 99%, purchased from Wuxi company of Xingda.
2 methyl pentamethylenediamine：Purity is 98%, purchased from TCI companies.
KI：Purity is 99%, purchased from Alfa companies.
Sodium iodide：Purity is 99%, purchased from Alfa companies.
Cuprous iodide：Purity is 99%, purchased from Alfa companies.
Cuprous bromide：Purity is 99%, purchased from Alfa companies.
Sodium hypophosphite（1 water）：Purity is 99%, purchased from Alfa companies.
Cuprous acetate：Purity is 99%, purchased from Alfa companies.
Magnesium stearate：Purity is 99%, purchased from Alfa companies.
Embodiment 1
（Prepared by the prepolymer of manufacture method 1, the melt polymerization of the prepolymer of manufacture method 2）
100ml toluene, then 10.630g (0.104mol) 1,5- penta into toluene solvant are added in 250ml three-neck flasks
Diamines, nitrogen starts to stir after purging, and adds 20.230g into this system again（0.100mol）Dibutyl oxalate.Then rise
Temperature continues back flow reaction 5 hours, filtering, to wash, be dried to obtain the prepolymer that relative viscosity is 1.27 to 130 DEG C, with the condition.
Gained 5.000g prepolymers and 0.010gKI are sufficiently mixed, are then fed to a diameter of 19mm teat glass
In, then with nitrogen replace 5 times repeatedly, be then placed into 325 DEG C of metal bath, depressurized with 20 minutes under nitrogen flowing
To below 100Pa, then it is set to react 40 minutes.Polymer property is in table 1.
Comparative example 1
Embodiment 1 is repeated, the difference is that without addition KI.Polymer property is in table 1.
Comparative example 2
Prepared by the prepolymer that the preparation of prepolymer is same as in embodiment 1, the preparation method of polymer is that preparation method 3 is pre-
The solid phase of polymers, 2g prepolymer is added in a diameter of 19mm teat glass, and enters line replacement with nitrogen.Then exist
Less than the 280 DEG C depressurized solid phase polymerizations for carrying out 5 hours, final pressure is 60Pa.Polymer property is in table 1.
Comparative example 3
It is prepared by PA66
3.559g (0.0306mol) hexamethylene diamine, 4.440g (0.0304mol) are added in a diameter of 19mm teat glass
Adipic acid and 4.530g deionized waters.Then this test tube is placed into autoclave, purged with nitrogen, then started to warm up, pressed
Power starts to raise.Pressure rises to 1.78MPa when temperature rises to 220 DEG C, and 1.78MPa pressure remains unchanged, in releasing system
Moisture content.Stop reaction after continuing reaction 2 hours, temperature now is 241 DEG C.The prepolymer in autoclave is taken out after cooling.It is dry
It is dry to obtain the prepolymer that relative viscosity is 1.38.
Gained 5.000g prepolymers and 0.010gKI are sufficiently mixed, are then fed to a diameter of 19mm teat glass
In, then with nitrogen replace 5 times repeatedly, be then placed into 282 DEG C of metal bath, depressurized with 20 minutes under nitrogen flowing
To below 100Pa, then it is set to react 40 points.Polymer property is in table 1.
Comparative example 4：
Comparative example 3 is repeated, the difference is that without addition KI.Polymer property is in table 1.
Comparative example 5
It is prepared by PA46
293.47g (3.33mol) butanediamine, 467.82g (3.20mol) adipic acids and 320g is added in 3L autoclaves to go
Ionized water.Purged with nitrogen, start stirring heating, pressure starts to raise.Pressure rises to 0.30MPa when temperature rises to 152 DEG C,
And 0.30MPa pressure remains unchanged, the moisture content in releasing system.When the moisture content of outflow reaches 250g, stop releasing moisture content, now
Temperature be 184 DEG C.Stop reaction after continuing reaction 30 minutes, now pressure is 1.14MPa, and temperature is 214 DEG C.Release high pressure
Prepolymer in kettle.It is dried to obtain the prepolymer that relative viscosity is 1.14.
Gained 5.000g prepolymers and 0.010gKI are sufficiently mixed, are then fed to a diameter of 19mm teat glass
In, then with nitrogen replace 5 times repeatedly, be then placed into 312 DEG C of metal bath, depressurized with 20 minutes under nitrogen flowing
To below 100Pa, then it is set to react 40 points.Polymer property is in table 1.
Comparative example 6
Comparative example 5 is repeated, the difference is that without addition KI, polymer property is in table 1.
Embodiment 2
Embodiment 1 is repeated, the difference is that addition NaI, polymer property is in table 2.
Embodiment 3
Embodiment 1 is repeated, the difference is that addition CuI, polymer property is in table 2.
Embodiment 4
Embodiment 1 is repeated, the difference is that addition CuBr, polymer property is in table 2.
Embodiment 5
Embodiment 1 is repeated, the difference is that addition CuI/KI, polymer property is in table 2.
Comparative example 7
Embodiment 1 is repeated, the difference is that addition sodium hypophosphite.Polymer property is in table 2.
Comparative example 8
Embodiment 1 is repeated, the difference is that addition cuprous acetate.Polymer property is in table 2.
Comparative example 9
Embodiment 1 is repeated, the difference is that addition magnesium stearate.Polymer property is in table 2.
Comparative example 10
Embodiment 1 is repeated, the difference is that KI addition, polymer property is in table 3.
Embodiment 6
Embodiment 1 is repeated, the difference is that KI addition, polymer property is in table 3.
Embodiment 7
Embodiment 1 is repeated, the difference is that KI addition, polymer property is in table 3.
Embodiment 8
Embodiment 1 is repeated, the difference is that KI addition, polymer property is in table 3.
Embodiment 9
Embodiment 7 is repeated, diamines is the mixture of 1,5- pentanediamines and 1,6- hexamethylene diamine by a certain percentage, polymer property
In table 5
Embodiment 10
Embodiment 7 is repeated, diamines is 1,5- pentanediamines and 2- methyl isophthalic acids, the mixture of 5- pentanediamines by a certain percentage, is gathered
Compound characteristic is in table 5
Embodiment 11
Embodiment 7 is repeated, diamines is the mixture of 1,5- pentanediamines and 1,10- decamethylene diamine by a certain percentage, and polymer is special
Property is in table 5.
Embodiment 12
Repeat embodiment 7, diamines is 1,6- hexamethylene diamines and 2- methyl isophthalic acids, 5- pentanediamines, its molar ratio be 70/30 it is mixed
Compound, polymer property is in table 5.
Embodiment 13
Repeat embodiment 7, diamines is 1,6- hexamethylene diamines and 2- methyl 1,5- pentanediamines, its molar ratio be 90/10 it is mixed
Compound, polymer property is in table 5.
Comparative example 11
Embodiment 1 is repeated, diamine unit source is 1,9- nonamethylene diamines and no addition KI, and polymer property is in table 4.
Comparative example 12
Embodiment 1 is repeated, diamine unit source is 1,9- nonamethylene diamines, and polymer property is in table 4.
Comparative example 13
Embodiment 1 is repeated, diamine unit source is 1,10- decamethylene diamines and no addition KI, and polymer property is in table 4.
Comparative example 14
Embodiment 1 is repeated, diamine unit source is 1,10- decamethylene diamines, and polymer property is in table 4.Table 1
Table 1 is continuous
In table 1, for PA52, the relative viscosity for adding the polymer after KI is much improved, but for making
For comparative polymers PA66 and PA46, the relative viscosity for adding the polymer after KI is not improved, therefore KI pairs
PA52 high polymerization degree has special result.In addition, compare from embodiment and comparative example 2 it can be seen that KI melts to PA52
Melting delay stability has special effect.
Table 2
Table 2 is continuous
In table 2, above-mentioned metal halide is added in PA52, and the viscosity of polymer is improved and heat resistance is all special
Effectively, but as polyamide heat stabilizer sodium hypophosphite commonly used etc. reduces PA52 heat resistance.
Table 3
Table 4
In table 4, the fusing point of PA52 polymer is 304 DEG C, and add the polymer after KI have high relative viscosity and
Stability is detained in good melting, but for as comparative polymers PA92 and PA102, even if not adding KI etc.
Metal halide, relative viscosity and good melting that can also be high be detained stability.
Table 5
Table 5 is continuous
Claims (9)
- A kind of 1. polyamide containing diamine unit and two acid units, it is characterised in that:The fusing point of the polyamide is at 280 DEG C More than；50~100 moles of % of two acid unit therein are oxalic acid units；Contain cuprous iodide, copper bromide, cuprous bromide, chlorine Change copper, stannous chloride, manganous chloride, manganese dibromide, manganous diiodide, zinc iodide, zinc bromide, zinc chloride, KI, KBr, It is one or more in potassium chloride, sodium iodide, sodium chloride, sodium bromide, lithium chloride, lithium iodide or lithium bromide；Relative to polyamide resin The weight of fat, the content of metal is 100~4000ppm；Stood in nitrogen atmosphere at a temperature of than fusing point high 20 DEG C and be detained 60 Minute when sulfuric acid solution relative viscosity be set to Y, when the sulfuric acid solution relative viscosity before delay is set to X, Y/X be 0.85~ 1.40。
- 2. polyamide according to claim 1, it is characterised in that:10~100 moles of % of diamine unit are 1,5- Pentanediamine unit.
- 3. polyamide according to claim 1, it is characterised in that:Using 96% sulfuric acid as solvent, concentration is The relative viscosity that 0.01g/ml polyamide sulfuric acid solution determines at 25 DEG C is 2.05~5.00.
- 4. polyamide according to claim 1, it is characterised in that:Amide groups molal quantity in 1g polyamide is 9.5 ~14.5mmol.
- 5. polyamide according to claim 1, it is characterised in that:Using differential scanning calorimeter, in nitrogen atmosphere Under, after dropping to 30 DEG C under molten condition with 20 DEG C/min of cooling rate, then when being warming up to more than fusing point with 20 DEG C/min The melting enthalpy change (Δ Hm) observed is 65~150J/g.
- 6. polyamide according to claim 1, it is characterised in that:By the thickness of the polyamide be 0.1~ When 0.5mm film is completely immersed in 23 DEG C of deionized water, its saturation hydroscopicity is less than 4.5wt%.
- A kind of 7. method for preparing the polyamide any one of claim 1-6, it is characterised in that including following step Suddenly:Diamine source and dicarboxylic acids source are carried out step (a) into solution or melt polymerization obtains low molecular weight prepolymer, wherein two 50~100 moles of % of first carboxylic acid are oxalic acid units；Step (b) carries out melt polymerization to prepolymer or solid phase obtains polyamide；Wherein:Cuprous iodide, copper bromide, cuprous bromide, copper chloride, stannous chloride, manganous chloride, manganese dibromide, manganous diiodide, Zinc iodide, zinc bromide, zinc chloride, KI, KBr, potassium chloride, sodium iodide, sodium chloride, sodium bromide, lithium chloride, lithium iodide, Or one or more are to be added in step (a) or in the incipient stage of step (b) in preparation process in lithium bromide.
- 8. Amilan polyamide resin composition, it is characterised in that:Relative to polyamide according to any one of claims 1 to 6 100 weight portions coordinate the Amilan polyamide resin composition of 0.1~200 weight portion packing material.
- 9. Amilan polyamide resin composition, it is characterised in that:Relative to polyamide according to any one of claims 1 to 6 100 weight portions coordinate the Amilan polyamide resin composition of the packing material of 5~100 weight portion impact resistances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310525548.3A CN103865058B (en) | 2012-12-17 | 2013-10-30 | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105497280 | 2012-12-17 | ||
| CN201210549728 | 2012-12-17 | ||
| CN201210549728.0 | 2012-12-17 | ||
| CN201310525548.3A CN103865058B (en) | 2012-12-17 | 2013-10-30 | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103865058A CN103865058A (en) | 2014-06-18 |
| CN103865058B true CN103865058B (en) | 2017-12-15 |
Family
ID=50904106
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310247935.5A Pending CN103865057A (en) | 2012-12-17 | 2013-06-20 | Polyamide resin, preparation method thereof and polyamide resin composition |
| CN201310525548.3A Active CN103865058B (en) | 2012-12-17 | 2013-10-30 | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310247935.5A Pending CN103865057A (en) | 2012-12-17 | 2013-06-20 | Polyamide resin, preparation method thereof and polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103865057A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865057A (en) * | 2012-12-17 | 2014-06-18 | 东丽先端材料研究开发（中国）有限公司 | Polyamide resin, preparation method thereof and polyamide resin composition |
| CN105440281B (en) * | 2014-09-23 | 2019-02-26 | 东丽先端材料研究开发（中国）有限公司 | A kind of polyamide, preparation method and its molded product |
| US20170321029A1 (en) * | 2014-11-19 | 2017-11-09 | Toray Industries, Inc. | Thermoplastic polyester resin composition and molded article |
| CN104830054B (en) * | 2015-03-26 | 2018-05-18 | 金发科技股份有限公司 | A kind of daiamid composition |
| CN107629205A (en) * | 2017-10-20 | 2018-01-26 | 广州市万佳成塑料有限公司 | A kind of production method of the low molecule amount nylon 46 powder synthesis resin of high molecular weight nylon 46 |
| CN112143227A (en) * | 2019-06-27 | 2020-12-29 | 住友化学株式会社 | Optical film, flexible display device, and method for manufacturing optical film |
| CN111875957A (en) * | 2020-06-29 | 2020-11-03 | 金发科技股份有限公司 | Polyamide composition and preparation method and application thereof |
| CN115926150A (en) * | 2021-08-30 | 2023-04-07 | 上海凯赛生物技术股份有限公司 | Polyamide resin and preparation method thereof |
| CN115772262B (en) * | 2021-09-06 | 2024-01-19 | 成都肆零壹科技有限公司 | Continuous process for preparing aliphatic dibasic acid nylon |
| CN115886409A (en) * | 2022-12-06 | 2023-04-04 | 苏州宏可菲材料科技有限公司 | High-temperature-aging-resistant anti-slip magic tape and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19847627A1 (en) * | 1998-10-15 | 2000-04-20 | Brueggemann L Kg | Copper salt-based stabilizer for polyamides for electrical and electronics industries comprises complex with phosphine and/or mercaptobenzimidazole compound and at least one halogenated organic compound |
| US8674055B2 (en) * | 2009-02-26 | 2014-03-18 | Toray Industries, Inc. | Method for producing polyamide resin |
| US8975364B2 (en) * | 2010-04-30 | 2015-03-10 | Ube Industries, Ltd. | Polyamide resin |
| JP5482426B2 (en) * | 2010-05-13 | 2014-05-07 | 宇部興産株式会社 | Method for producing polyoxamide resin by solid phase polymerization |
| US20130065004A1 (en) * | 2010-05-17 | 2013-03-14 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| MX340553B (en) * | 2010-05-17 | 2016-07-14 | Mitsubishi Gas Chemical Co | Polyamide resin composition. |
| CN103403094B (en) * | 2011-02-24 | 2016-01-06 | 三菱瓦斯化学株式会社 | Masterbatch and utilize masterbatch to manufacture the method for Amilan polyamide resin composition |
| CN103865057A (en) * | 2012-12-17 | 2014-06-18 | 东丽先端材料研究开发（中国）有限公司 | Polyamide resin, preparation method thereof and polyamide resin composition |
-
2013
- 2013-06-20 CN CN201310247935.5A patent/CN103865057A/en active Pending
- 2013-10-30 CN CN201310525548.3A patent/CN103865058B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103865057A (en) | 2014-06-18 |
| CN103865058A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865058B (en) | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition | |
| JP6328629B2 (en) | Novel polyamide, process for its preparation and use thereof | |
| KR101800771B1 (en) | Method for producing polyamide | |
| CN1390887A (en) | Polyamide composition | |
| JP2016528312A (en) | Process for continuously producing aliphatic or partially aromatic polyamides | |
| CN103421185A (en) | Aliphatic polyamide resin and use thereof | |
| CN105440281B (en) | A kind of polyamide, preparation method and its molded product | |
| CN104059224B (en) | A kind of polyamide and preparation method thereof and Amilan polyamide resin composition | |
| PT3008106T (en) | Partially aromatic copolyamides with a high glass transition temperature and high degree of crystallinity | |
| JP2007332353A (en) | Polyamide resin | |
| JP3525607B2 (en) | Polyamide resin composition | |
| CN105085901B (en) | A kind of polyamide and its manufacturing method | |
| CN102660019B (en) | High temperature-resistant nylon/ polybutylece terephthalate (PBT)/polyethylene terephthalate (PET) copolymer, and preparation method and application thereof | |
| CN101346412B (en) | High melting point polyamide | |
| CN102660020B (en) | High-temperature resistant nylon/PEN/PBT/PET copolymer and preparation method thereof | |
| CN102660018B (en) | High temperature-resistant nylon/polyethylenenaphthalate (PEN) /polyethylene glycol terephthalate (PBT) copolymer, and preparation method and application thereof | |
| JP3458544B2 (en) | Copolyamide and method for producing the same | |
| KR102203359B1 (en) | Xylylene diamine composition, and method for producing polyamide resin | |
| CN102604081A (en) | High-temperature resistant nylon/ polyethylene terephthalate (PET) copolymer, preparation method and application thereof | |
| CN103172853B (en) | A kind of aliphatic polyamide resin and application thereof | |
| JP2015178551A (en) | Method of producing diamine-dicarboxylic acid salt aqueous solution | |
| JP3525606B2 (en) | Polyamide resin composition | |
| CN102634012B (en) | Heat resisting polyamide/PEN (polyethylene naphthalate)/PET (polyethylene terephthalate) copolymer and manufacturing method and application of heat resisting polyamide/PEN/PET copolymer | |
| KR102192621B1 (en) | Xylylenediamine composition and method for producing polyamide resin | |
| CN102618025A (en) | High-temperature resistant nylon/PEN copolymer and preparation method as well as application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |